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Doping topological Dirac semimetal with magnetic impurities: Electronic structure of Mn-doped Cd 3 ⁢As 2

The prospect of transforming a Dirac topological semimetal (TSM) into a Weyl TSM phase, following doping by magnetic impurities, is central to TSM applications. The magnetic field from polarized 𝑑 levels of magnetic impurities produces a field with a sharp local structure. To what extent magnetic impurities act in the same manner as an applied field and what are the effects of such a field on the electronic structure of a Dirac TSM are the subject of this paper. We present electronic structure calculations of bulk Cd 3 ⁢As 2 with substitutional doping of Mn impurities in the dilute alloy range. Quasiparticle 𝐺⁡𝑊 (QS⁢𝐺⁡𝑊) ab initio electronic structure calculations are used in conjunction with 𝑘 · 𝑝 model Hamiltonian calculations. As expected, we observe the splitting of the Dirac points into pairs of Weyl points following the doping with Mn. We also show that the electronic structure of Mn-doped Cd 3⁢ As 2 can be emulated by the electronic structure of pristine Cd 3⁢ As 2 with an appropriate external magnetic field. Some properties of the conductivity of bulk Cd 3 ⁢As 2 for different magnetic field orientations are also investigated. Our results inform future opportunities for unique device functionality based on band structure tuning not found in conventional magnetic Weyl TSM.

36 MATERIALS SCIENCE↗

Dynamic Interaction of Grid-Forming and Grid-Following Inverters with Synchronous Generators in Hybrid Power Plants

As the integration of renewable energy resources such as wind and solar generation continues to grow, the use of hybrid power plants with both synchronous machines and power electronic inverters operating in parallel becomes more common. This paper studies the impact on small-signal stability for these pairs of devices, first as an isolated two-device system and then as part of a 9-bus test system. Each operational scenario was studied with both a grid-following inverter and a grid-forming inverter. In each scenario, the state variables associated with the synchronous generator's excitation system were found to be responsible for the inception of instability. These results underscore the importance of accurate modeling of excitation systems when modeling power systems with hybrid power plants.

hybrid power plant↗

Co nanoclusters derived from zinc-trimesic acid fiber for efficient levulinic acid hydrogenation

The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is significant for producing chemicals and fuels from renewable resources, a promising direction in biomass refining. Currently, non-precious metal catalysts suffer from low activity due to a single electronic structure, which is incapable of effectively activating both CO in LA and H 2 . Herein we report in situ fabricated Co nanoclusters within positive and metallic Co sites on N-doped carbon, which can simultaneously activate LA's CO and H 2 , enhancing the activity and selectivity for GVL production. Urea-assisted Co dispersion coupled with variation of pyrolysis temperature, Co nanoclusters were formed via direct conversion of Co-containing zinc trimesic acid fibers. The resulting Co nanoclusters possess dual active sites of Co-N x and metallic Co, with adjustable electronic structures. Under the reaction conditions of 200 °C and 4.5 MPa H 2 for 4 h, LA was completely converted, achieving 95 % yield of GVL. The outstanding catalytic activity is attributed to the Co-N x and metallic Co active sites, which facilitate the activation of CO and H 2 , respectively. In conclusion, this research provides a new concept for converting N-free metal-organic frameworks into non-precious metal nanoclusters, offering valuable insights for designing high-performance non-precious metal catalysts for biomass-derived chemical and fuel production.

Co nanoclusters↗

Soft-Switching Solid-State Transformer With Reduced Conduction Loss

Solid-state transformers (SSTs) are a promising solution photovoltaic (PV), wind, traction, data center, battery energy storage system (BESS), and fast charging electric vehicle (EV) applications. The traditional SSTs are typically three-stage, i.e., hard-switching cascaded multilevel rectifiers and inverters with dual active bridge (DAB) converters, which leads to bulky passives, low efficiency, and high electromagnetic interference (EMI). This article proposes a new soft-switching solid-state transformer (S4T). The S4T has full-range zero-voltage switching (ZVS), electrolytic capacitor-less dc link, and controlled dv/dt, which reduces EMI. The S4T comprises two reverse-blocking current-source inverter (CSI) bridges, auxiliary branches for ZVS, and transformer magnetizing inductor as a reduced dc link with 60% ripple. Compared with the prior S4T, an effective change on the leakage inductance diode is made to reduce the number of the devices on the main power path by 20% for significant conduction loss saving and retain the same functionality of damping the resonance between the leakage and resonant capacitors and recycling trapped leakage energy. The conduction loss saving is crucial, being the dominating loss mechanism in SSTs. Importantly, the proposed single-stage SST not only holds the potential for high power density and high efficiency but also has full functionality, e.g., multiport dc loads integration, voltage regulation, and reactive power compensation, unlike the traditional single-stage matrix SST. The S4T can achieve single-stage isolated bidirectional dc–dc, ac–dc, dc–ac, or ac–ac conversion. It can also be configured input-series output-parallel (ISOP) in a modular way for medium-voltage (MV) grids. Hence, the S4T is a promising candidate for the SST. The full functionality, e.g., voltage buck–boost, multiport, etc., and the universality of the S4T for the dc–dc, dc–ac, and ac–ac conversion are verified through the simulations and experiments of two-port and three-port MV prototypes based on 3.3 kV SiC MOSFETs in dc–dc, dc–ac, and ac–ac modes at 2 kV.

14 SOLAR ENERGY↗

Wide Bandgap Generation (WBGen): Developing the Future Wide Bandgap Power Electronics Engineering Workforce

This Final Technical Report (FTR) summarizes the work conducted at the Center for Power Electronics Systems (CPES) under the Wide-Bandgap Generation (WBGen) fellowship and traineeship program established by the Advanced Manufacturing and Technologies Office (AMMTO) of the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy (EERE) at Virginia Tech, which had as main objective to train the next generation of U.S. citizen power engineers with wide-bandgap (WBG) power semiconductor expertise, with the intent to aid in fulfilling the future workforce needs in this field. The latter was deemed of strategic importance given the fast-paced growth observed—and predicted—in the demand of this technical expertise, whose practitioners have become the enablers and executioners of the electrification transformation process that not just the U.S., but the whole world, is currently undergoing as it seeks for more effective and efficient ways to use energy. As such, the WBGen program set forth to achieve its educational goals, which in addition sought to broaden the range of WBG-based power electronics by conducting research and development on high-efficiency grid apparatus and high-efficiency electrical power systems, and to also enhance the power engineering curriculum by formalizing WBG-oriented design procedures replacing existent yet now obsolete design procedures developed for Silicon (Si) based power electronics. This effort led CPES to spearhead the development of a new major within The Bradley Electrical and Computer Engineering (ECE) Department at Virginia Tech, namely Electronic Power and Energy Systems (EPES), which coalesced power electronics and power systems courses to provide undergraduate students with a strong formation in the power engineering field, while creating a pipeline of graduate students that could pursue the WBG-based curriculum and conduct research at CPES. In all, in what is considered a true success, eight of the twenty WBGen fellows that graduated program were recruited from the ECE department undergraduate cohort. The traineeship emphasized as well, from its beginning, the partnership with industry and national laboratories, which took advantage of the successful industry consortium at CPES that has historically been formed by 80–90 power and energy companies working in close collaboration with the center. This gave WBGen fellows the accessibility and possibility to conduct internships at partner facilities during the summer months, focused solely on the evaluation, testing, and adoption of WBG devices, which were many times tightly related to their respective research work and plans. In addition, WBGen fellows conducted their main research work within the confines of research programs at CPES conducted with these industry partners, providing them with a unique opportunity to develop not just their technical expertise—while advancing their knowledge, but to also learn and practice a slew of skills needed for their professional growth. As such, the fellows tackled a variety of WBG-related research topics, from device reliability and capability aspects as well as packaging and integration, encompassing the use of advanced materials and new structures, current sharing challenges, and insulation systems, to advanced gate-drivers with integrated sensors and protection mechanisms and active current- and voltage-based control, to optimized layouts seeking to maximize the switching and power processing performance of these devices, to power processing solutions adopting Gallium-Nitride (GaN) and Silicon-Carbide (SiC) power semiconductors for a variety of applications; including radiation-hardened converters for space dc distribution systems, direct three-phase ac-to-ac power converters for aerospace systems, dc-ac inverters for automotive traction drives, high-frequency isolated dc-dc battery chargers also for heavy transportation systems, and medium-voltage dc-dc and dc-ac converters for distribution systems and future power grids. The WBGen program ultimately graduated a total of 20 power engineers, all experts on WBG-based power electronics, awarding 18 M.S. and 2 PhD degrees in the process. These fellows, all U.S. citizens, allowed CPES to increase the number of citizens students to 33 % at the peak of the program, as the traineeship made possible the recruitment of talent with more attractive graduate research assistantship (GRA) contracts. Unfortunately, the present U.S. citizen enrollment at CPES has declined back to historic levels—approximately 10 %, as the regular GRA rates are not competitive enough when compared with entry-level industry jobs. In all, WBGen fellows published a total of 7 peer-reviewed journal articles, 44 papers at international technical conferences, made 42 presentations at international technical conferences, and filed 4 invention disclosures and patent applications, which have since then been granted by the U.S. Patent and Trademark Office (USPTO). Their contribution to CPES, Virginia Tech, the United States, and the world, has been significant, and continues to yield results thanks to the exemplary career that the fellows have initiated at many of the partners of the program, which include Wolfspeed, Raytheon Technologies, Infineon, Lockheed Martin, Dominion Energy, Northrop Grumman, Rivian, Aerospace Corporation, Sandia National Laboratory, National Renewable Energy Laboratory, John Hopkins University, and Virginia Tech.

14 SOLAR ENERGY↗

Shape-Controlled NaTaO 3 by Flux-Mediated Synthesis

NaTaO 3 is a stable and wide bandgap n-type semiconductor material with many different applications. Here, a flux-mediated synthesis method is presented for NaTaO 3 resulting in highly distinctive, substrate covering shapes via precursor chemistry variation at comparatively low temperatures. It is found that the microstructure of the resulting NaTaO 3 films can be varied from nanocubes to smooth thin films. These shapes and surface chemistries can be correlated by employing density functional theory calculations and surface sensitive X-ray photoemission spectroscopy. This study provides guidance on how to synthesize the material and tailor its shape and surface termination for different applications. Finally, as a proof of concept of one possible application, NaTaO 3 is applied to perovskite solar cells as the electron transport layer, resulting in conversion efficiencies of >19%. Further, this study provides a new strategy for designing ternary oxide thin films for renewable energy applications.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Grid-tied Multilevel Inverter with Phase-locked Loop Algorithm

A multilevel inverter is an electronic device capable of changing direct current energy to alternant current energy with a voltage and frequency established by the user. They are ideal for connecting renewable energy sources to the AC grid, energy plants, and smart grids. The voltage must be balanced and synchronized with the electrical network for adequate performance. This paper shows the voltage synchronization between an inverter output voltage and the AC grid using a phase-locked loop based on an adaptive observer. The proposed algorithm can perform under grid uncertainties such as noise and generates a reference signal for the modulation used in the inverter. The algorithm is robust and computationally efficient and can be implemented through basic elements such as operational amplifiers, resistors, and capacitors, reducing its difficulty in executing it in a system.

42 ENGINEERING↗

Electrical Systems of Pumped Storage Hydropower Plants: Electrical Generation, Machines, Power Electronics, and Power Systems

Adjustable-speed (AS) pumped storage hydropower (PSH) technology has the potential to become a large, consistent contributor to grid stability enabling higher penetrations of wind and solar energy on the future U.S. power system. AS-PSH has high-value characteristics, such as fast response to provide ancillary services to the grid, because it is a power converter interface with the grid (like battery storage), but at the same time it has the energy content large enough to supply both short-term (seconds-to-minutes) and long-term (minutes-to-hours) of energy needs, like more conventional power plants. However, designs must be optimized to lower the capital expenditure (CapEx) and to provide a high-quality grid interface capability (e.g. power quality, ancillary service provider, fault-tolerant or fault ride-through capability), which is a primary factor in the acceptance of AS-PSH into a utility’s generation mix. This CapEx will be greatly affected by the cost savings associated with the civil structure, turbine design, power electronics, control systems, or unique generator designs. A holistic design must be considered to get a full picture of the benefits of the technology proposed. The AS-PSH can be controlled to reduce the impact of transient disturbance on a power system and at the same time can be controlled to minimized subsequent component fatigue and potential oscillation modes within the plant, with the overall impact in reducing the operational expenditures (OpEx).Generating clean power to meet standards such as Institute of Electrical and Electronics Engineers (IEEE) 519 and International Electrotechnical Commission (IEC) 1000-3-2 will be a continuing challenge. For many technology developers, however, improved AS-PSH technologies will become a key component of generator-storage systems of the future given the prospects of increased performance and decreasing costs, and the ever-increasing penetration of renewables (e.g wind power and solar power).

13 HYDRO ENERGY↗

Investigating the Electronic Structure of Prospective Water-Splitting Oxide BaCe 0.25 Mn 0.75 O 3-δ before and after Thermal Reduction

BaCe 0.25 Mn 0.75 O 3-δ (BCM), a non-stoichiometric oxide with a layered perovskite-like crystal structure, has recently emerged as a prospective contender for application in renewable energy harvesting by solar thermochemical hydrogen generation. Using solar-thermal energy and a reducing environment, oxygen vacancies can be created in high-temperature BCM, and the reduced crystal so obtained can, in turn, produce H 2 by stripping oxygen from H 2 O. Therefore, a first step toward understanding the working mechanism and optimizing the performance of BCM is a thorough and comparative analysis of the electronic structure of the pristine and the reduced material. In this paper, we probe the electronic structure of BCM using the combined effort of first-principles calculations and experimental O K-edge X-ray absorption spectroscopy (XAS). The computed projected density of states (PDOS) and orbital plots are used to propose a simplified model for orbital mixing between the oxygen and metal atoms. With the help of state-of-the-art simulations, we are able to find the origins of the XAS peaks and categorize them on the basis of contribution from Ce and Mn. For the reduced crystal, the calculations show that the change in electron density resulting from the reduction is strongly localized around the oxygen vacancy. Experimental measurements reveal a marked lowering of the first O K-edge peak in the reduced crystal. Using theoretical analysis, this is shown to result from lifting of spin degeneracy in the absorption peaks as well as from a diminished O 2p contribution to the frontier unoccupied orbitals, in accordance with the tight binding scheme. The simulated results serve as a reference for the extent of spectral change as a function of the percentage of oxygen vacancies in the reduced crystal. Here, our study paves the way for the investigation of the working mechanism of BCM and for computational and experimental efforts aimed at design and discovery of efficient water-splitting oxides.

08 HYDROGEN↗

Synthesis and Reactivity of Fe(II) Complexes Containing Cis Ammonia Ligands

The development of earth-abundant transition-metal complexes for electrocatalytic ammonia oxidation is needed to facilitate a renewable energy economy. Important to this goal is a fundamental understanding of how ammonia binds to complexes as a function of ligand geometry and electronic effects. Here, we report the synthesis and characterization of a series of Fe(II)–NH 3 complexes supported by tetradentate, facially-binding ligands with a combination of pyridine and N-heterocyclic carbene donors. Electronic modification of the supporting ligand led to significant shifts in the Fe III/II potential and variations in NH bond acidities. Finally, investigations of ammonia oxidation by cyclic voltammetry, controlled potential bulk electrolysis, and through addition of stoichiometric organic radicals, TEMPO and tBu3 ArO • are reported. No catalysis of oxidation of NH 3 to N 2 was observed, and 15 N 2 was detected only in reactions with tBu3 ArO • .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Organizational Influence on Supply Chain for Digital Energy Infrastructure: Business Models, and Policy Landscape

Significant investment is driving the essential modernization and digitization of U.S. energy infrastructure, but the United States faces a key challenge in this grid transformation: our renewable and clean energy supply chains have limited capacity to source necessary digital assets through U.S. or allied sources. Batteries and their associated power electronic interfaces are key components to delivering clean and more resilient energy delivery, providing much-needed fast ramping, emergency discharge, generation, and operations support to the electric grid. These services have grown to be invaluable over the past 10 years and will soon be an irreplaceable component of energy delivery. While there have been significant strides to move supply chains for raw and critical materials to U.S. and allied nations, the control and power electronic industry has lagged, in part because of lower cost margins. For example, the United States now has growing capacity to manufacture solar photovoltaic (PV) panels, but 90% of the inverters—which are essential to the conversion of DC to AC for grid connection and controls—are made in or source parts from the People’s Republic of China (PRC). While a global supply chain is beneficial for many economic and supply diversification reasons, presence of foreign entities of concern (FEOC) in a dominant role in this supply chain brings additional concerns for national security of infrastructure. The BESS relationship and new clean energy have features that warrant discussions and additional focus on impact for technology security, given their critical role. This review considers the impact and solutions for complex business and policy landscapes in clean energy supply chain, and the benefit trade-offs, focusing on the Battery Energy Storage System case study, and its complex organizational relationships across both the US, Allied countries and Foreign Entities of Concern. While many examples in this paper are presented on PRC focused manufacture, this could apply to any potentially adversarial relationship

25 - ENERGY STORAGE↗

Hardware-in-the-Loop Efficiency Analysis of Tidal Power Systems

Marine renewable energy presents an opportunity for sustainable power in areas located near and in the marine environment. In particular, tidal energy offers a consistent and reliable resource. However, tidal energy harvesting systems seeking to take advantage of this resource face challenges associated with power electronics. Power conversion electronics struggle with low efficiencies, lack of off-the-shelf options for small-scale energy harvesting systems, and limited opportunities for testing with deployed turbines. This work demonstrates a hardware-in-the-loop experimental design and methodology for characterizing efficiency of tidal turbine power electronics and control methods. The suggested method removes barriers to testing these power electronics by eliminating the need for a physical tidal turbine and generator to produce accurate harvested tidal power profiles.

tidal turbine, hardware-in-the-loop, energy conver↗

A Hot‐Swappable, Fault‐Tolerant, Modular Power Converter System for Solar Photovoltaic Plants

The performance metrics of the state-of-the-art commercial solar inverters, such as system cost, operation and maintenance (O&M) cost, service life, reliability, maintainability, and power density are much lower than the target metrics needed to achieve SunShot’s 2030 levelized cost of energy (LCOE) goals. To overcome the shortcomings of the existing solar inverters, this project proposed a novel Hot-Swappable, Fault-Tolerant, Modular Power Converter (HSFT-MPC) concept for solar photovoltaic (PV) plants and proved the concept through the design, fabrication, and laboratory test validation of a single-phase HSFT-MPC prototype. The HSFT-MPC has the following distinct advantages over the state-of-the-art: 1) elimination of harmonic/ electromagnetic interference (EMI) filter in the inverter stage due to the novel topology, 2) lower system cost and higher power density due to the modular design, elimination of harmonic/EMI filter, and lower cooling requirement, 3) higher efficiency due to lower switching frequencies, 4) higher reliability and longer (50 years) service life due to simpler cooling and fault tolerance capability, 5) easier installation, lower O&M cost, and improved maintainability due to the modular design and hot-swappable power electronic building blocks (PEBBs), and 6) improved manufacturability due to the modular design. This project developed a single-phase HSFT-MPC prototype with 25kW nominal output power, 2.4kV, 60Hz nominal AC output, lower than 5% AC output voltage total harmonic distortion, over 5 kW/L inverter power density, and 99.4% inverter peak efficiency, being tolerant to failure of single and multiple PEBBs, and capable of hot swapping of the failed PEBB(s). The HSFT-MPC enables uninterruptable operation of the solar PV plant when failure of single or multiple PEBBs or PV modules occurs. Compared with the existing solar inverters in the market, the HSFT-MPC is expected to reduce the inverter failure-caused downtime and energy losses of solar PV plants by more than 60% and 50%, respectively. Project findings have been presented at major conferences in the field and published in peer-reviewed papers, which added new knowledge to the field of power electronics for solar PV systems. A minicourse on Solar PV Systems was developed for outreach activities. The minicourse will help attract young individuals to the renewable energy profession which has a significant talent shortage. The HSFT-MPC is expected to overcome all of the shortcomings of the state-of-the-art solar inverters in terms of cost, efficiency, service life, reliability, maintainability, and manufacturability targets needed to achieve SunShot’s 2030 LCOE goals. Therefore, the proposed HSFT-MPC concept has the great potential to disrupt the current solar inverter market. This project created a pathway towards industry adoption of the HSFT-MPC to help achieve 50-year service life solar PV systems. Since the solar PV plants using the HSFT-MPC will feature with higher reliability, longer service life, and easier maintenance, they are particularly useful for the rural areas with underserved populations that demand reliable and affordable clean electricity. The outcomes of the project have the strong potential to address national needs in the field of renewable energy to reduce CO 2 emissions from the electricity sector, reduce imports of energy from foreign sources, and improve energy security, efficiency, and sustainability. Since electricity is used in almost all of society’s sectors, the outcomes of the project will benefit various sectors of society and economy.

14 SOLAR ENERGY↗

Survey of the Polar Wind near 1 and 8Re with POLAR

Recent theoretical/modeling developments as well as measurements by Akebono and other spacecraft have created renewed interest in the polar wind. This interest arises generally from two principal aspects: (a) Understanding the physics of such plausible influences as photo-electron-driven parallel electric fields and convection-driven centrifugal acceleration on the polar wind transport; and (b) Understanding the intermediate fate of the polar wind--in particular, its contribution to the plasma content of such magnetospheric domains as the plasma sheet and tail lobes. In this talk, we will describe the results of a new survey of the intermediate(lR(sub E)) and high(8 R(sub E)) polar wind, based on high-resolution core ion measurements with the Thermal Ion Dynamics Experiment(TIDE) on POLAR. These new measurements of H(+), He(+), and O(+) densities, parallel flow velocities, Mach numbers and fluxes, and parallel and perpendicular temperatures, will be used to explore such issues as: (1) Supersonic vs. subsonic polar wind flows; (2) Upward and downward O(+) flows, and the origin of the polar cap ions; (3) Parallel flow speeds for various polar wind ion species in the context of various acceleration/transport mechanisms; and (4) Relationships of polar wind bulk parameters to solar zenith angle and to magnetospheric day-night distance, and their implications for the origin and transport of the polar wind.

Horwitz, J. L.↗

PowerAmerica (Final Technical Report)

The U.S. Department of Energy’s Advanced Manufacturing Office (predecessor to AMMTO) established PowerAmerica in December 2014 to develop and accelerate the adoption of wide bandgap (WBG) semiconductor chips and power electronics in manufacturing. The objective was to spark early commercialization of energy efficient products; educate and train the workforce; create high-tech jobs; and nurture the growth of the U.S. WBG semiconductor manufacturing industry. PowerAmerica isled by North Carolina State University by way of a five-year, $140M cooperative agreement with DoE. This private-public partnership with DoE includes member companies ranging from startups and small-medium enterprises to large system integrators, world-class universities, and national labs. The WBG power electronic ecosystem formed by our diverse membership is focused on using advanced manufacturing to 1) lower the cost of silicon carbide and gallium nitride semiconductor devices to be comparable to silicon devices; 2) demonstrate the system benefits and energy efficiency advantages of WBG semiconductor power electronics through system demonstrations that validate their effectiveness; and 3) build an education pipeline for a skilled workforce to meet the future demand for emerging WBG semiconductor markets — and enhance U.S. economic competitiveness globally. PowerAmerica was initially funded in six budget periods, each lasting 12 to 18 months. By the end of Budget Period 6 (August 2023), PowerAmerica had achieved its major objectives in technology development, semiconductor device cost reduction, ecosystem growth and engagement, and education and workforce development. Through strategic foundry investments, we helped to establish the first U.S. SiC foundry (X-FAB) and supported a lab (Microchip) to start SiC volume production. We’ve helped bring together companies from different parts of the supply chain, resulting in several successful new partnerships and business relationships. Through projects with some of the largest manufacturers of energy-intensive equipment in the U.S. — John Deere, GE, United Technologies, Raytheon, Carrier, Toshiba, and others — we have successfully demonstrated the energy and system benefits of WBG technology. We have also harnessed the unique capabilities and facilities of national labs — the Naval Research Laboratory, National Renewable Energy Laboratory, and Argonne National Laboratory — to help solve challenging technical problems for industry. Thanks to our many webinars, tutorials, annual events, and presence at major energy and electronics conferences around the world, the PowerAmerica name has become synonymous with WBG technology advancement. The commercial interest in WBG technology is higher than ever; companies and governments around the world have announced hundreds of millions of dollarsin future investment to build capacity — and compete with silicon in many markets and applications. We have trained hundreds of engineering students, from universities across the U.S., through hands-on projects and WBG coursework. Working professionals have also benefited through the years from our many targeted short courses, tutorials, and technical webinars. In short, PowerAmerica has made great strides in each of our key objectives, and the organization has been operating without government or NC State

14 SOLAR ENERGY↗

Complex polycation redox material interfaced with renewable porous carbon for asymmetric supercapacitors

Mixed polycation transition metal ferrites are known to exhibit unique and superior characteristics for structural, electrical, magnetic, and optical applications. Although a few binary transition metal ferrites are found to be suitable for electrochemical energy storage application, ternary transition metal ferrites are not investigated for asymmetric supercapacitors (ASCs). Mixed polycation oxides are expected to have increased active sites that can facilitate proton and electron transfer impacting the redox reactions. Specific crystal structure and associated lattice parameters as well as surface and morphological characteristics can also influence the energy storage properties. This study for the first time reports a novel complex polycation redox material, (Cu p Mn q Zn r ) x Fe y O z and renewable pinewood (PW) derived porous carbon (POC) as electrodes for ASC. Both (Cu p Mn q Zn r ) x Fe y O z and PW-POC are subjected to electrochemical characterization and used in ASC configuration with aqueous KOH electrolyte. It is anticipated that the Faradaic characteristics of (Cu p Mn q Zn r ) x Fe y O z will make it to serve as a cathode while PW-POC with capacitive behavior will act as anode in ASCs. Relatively higher specific capacitance of > 200 F/g is observed for the (Cu p Mn q Zn r ) x Fe y O z reference electrode and fabricated ASCs. Capacitance retention rate is tested in 10,000 cycles for the working electrodes whereas for ASC, the stability tests are performed over 100 charging-discharging cycles exhibiting relatively higher capacitance retention. (Cu p Mn q Zn r ) x Fe y O z appears to be a promising material for a supercapacitor.

(CupMnqZnr)xFeyOz↗

Insight Into the High-Potential Branch of the Alternate Nad+-Dependent NADPH:Ferredoxin Oxidoreductase II (NfnII) from Pyrococcus Furiosus. Evidence for the Gating Step in Electron Bifurcation

We have investigated the rapid-reaction kinetics of the NAD+-dependent NADPH:ferredoxin oxidoreductase II (NfnII) from Pyrococcus furiosus, permitting a comparison with recent work done with the paralog NfnI from the same organism. The half-potentials of the electron-bifurcating L-FAD are highly crossed in both NfnI, meaning the potential for the quinone/semiquinone couple is significantly lower than that for the semiquinone/hydroquinone couple so that the semiquinone oxidation state is thermodynamically unstable. The same appears to be the case with NfnII on the basis of its similar behavior in transient absorption spectroscopy experiments and the absence of any evidence for FAD*- accumulation in the course of reductive titrations (which would be manifested as a transient increase in absorbance at ~380 nm)1. Reductive titrations with both the one-electron donor sodium dithionite and the obligate two-electron donor NADPH demonstrate that, in contrast to NfnI, little FADH* accumulates in the high-potential pathway of NfnII in the course of reduction, as reflected in the absence of a transient increase in absorbance in the 500-600 nm region. This indicates that the half-potentials of the S-FAD are crossed in NfnII by a minimum of 120 mV. Rapid-reaction experiments mixing oxidized NfnII with NADPH also show no evidence of S-FADH* accumulation. Furthermore, the enzyme is only partially reduced at the end of the reaction with NADPH, indicating that there is little electron transfer into the high-potential pathway of NfnII. When the reaction is carried out in the presence of the one-electron carrier ferredoxin, only approximately one equivalent of ferredoxin becomes reduced, in contrast to the maximum of three equivalents seen with NfnI. This is consistent with only a single electron bifurcation event taking place under these conditions with NfnII, with only a single high-potential electron passing into the [2Fe-2S] cluster of the high-potential pathway of NfnII but not progressing further to the S-FAD. This accounts for the observation that NfnII has greatly reduced bifurcating activity compared to NfnI. The lack of electron transfer into the S-FAD of NfnII due to its crossed half-potentials prevents successive bifurcation activity and indicates that electron transfer within the high-potential branch gates bifurcation activity in NfnI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗